Thiol compound derivative, hardening compositions containing these derivatives and molded articles thereof

Abstract

The present invention relates to a thiol compound derivative represented by the following formula (1), a curable composition containing the derivative, and a molded product made of the composition. More particularly, the invention relates to a thiol compound derivative which is added to a polymer having reactivity to a thiol derivative substituent to provide a curable composition, a curable composition containing the derivative and a crosslinkable halogen-containing crosslinking polymer, and a crosslinked molded product of the composition; wherein X 1 , X 2 and X 3 are each a group represented by the following formula (2)

1. A curable composition containing:
 a halogen-containing crosslinking polymer, and 
 a thiol compound derivative selected from the group consisting of: 
 
       
         
           
           
               
               
           
         
       
       having, in one molecule, at least one functional group represented by the following formula (17): 
       
         
           
           
               
               
           
         
       
       wherein
 A is an oxygen atom or a sulfur atom, 
 R 1  is a hydrogen atom, an alkyl group or a phenyl group, 
 R 2  is a group selected from the group consisting of the following groups (a) to (f), 
 R 3  is a hydrogen atom, an alkyl group or a phenyl group; 
 (a) a group selected from an alkyl group, a halogenated alkyl group, an alkyl group having at least one hydroxyl group, an alkenyl group, an alkynyl group and an aralkyl group, 
 b) a residue wherein a hydroxyl group is removed from a hydroxyl group-containing compound selected from alkylene glycol, dialkylene glycol, trialkylene glycol, tetraalkylene glycol, allyl alcohols, ketooximes, alkanolamines, dialkanolamines, trialkanolamines, trialkylsilanol, alicyclic alcohol and naphthyl alcohols, 
 (c) a group represented by the following formula (3):
   —CHY—CH 2 X  (3) 
 
 
       wherein X is any one of a halogen atom, an alkoxy group, an alkoxyalkoxy group, a dialkylamino group, a trialkylsilyl group, an acetoxy group and a piperidino group, and Y is a hydrogen atom or a halogen atom,
 (d) a group represented by the following formula (4): 
 
       
         
           
           
               
               
           
         
       
       wherein Z is any one of a hydrogen atom, a halogen atom, a nitro group, an amino group, an alkoxy group, an alkylamino group, a dialkylamino group, an alkyl group and an acyl group, and n is an integer of 1 to 3 and is a number of substituents Z bonded to the phenyl group skeleton in the formula (4),
 (e) a group represented by —CH 2 —C 6 H 5  or H —CHCH 3 —C 5 H 5 , and 
 (f) a group represented by the following formula (5) or (6):
   —R 4 -ACH═CH 2   (5) 
 
 
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 3  are the same as Rand R 3  in the formula (2), A is an oxygen atom or a sulfur atom, and R 4  is any one of —CH 2 —, —CH 2 —CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 OCH 2 —, —CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2—,    
       
         
           
           
               
               
           
         
       
     
     
       2. The curable composition as claimed in  claim 1 , wherein the functional group represented by the formula (17) is formed by reacting a compound having a thiol group (—SH) with a vinyl ether. 
     
     
       3. The curable composition as claimed in  claim 1 , wherein the thiol compound derivative is a compound represented by the formula (1) 
       
         
           
           
               
               
           
         
       
       wherein X 1 , X 2  and X 3  are each a group represented by the formula (2). 
       
         
           
           
               
               
           
         
       
     
     
       4. The curable composition as claimed in  claim 1 , wherein the thiol compound derivative is a compound represented by the following formula (8) 
       
         
           
           
               
               
           
         
       
       wherein X 1  and X 2  may be the same or different and are each a group represented by the formula (2). 
       
         
           
           
               
               
           
         
       
     
     
       5. The curable composition as claimed in  claim 1 , wherein the thiol compound derivative is a compound represented by the following formula (9) 
       
         
           
           
               
               
           
         
       
       wherein X 1  and X 2  may be the same or different and are each a group represented by the formula (2), and M is an alkali metal or an alkaline earth metal. 
       
         
           
           
               
               
           
         
       
     
     
       6. The curable composition as claimed in  claim 1 , wherein the thiol compound derivative is a compound represented by the following formula (10): 
       
         
           
           
               
               
           
         
       
       wherein X 1  and X 2  may be the same or different and are each a group represented by the formula (2), A, R 1 , R 2  and R 3  are the same as A, R 1 , R 2  and R 3  in the formula (2), and R 5  is the same as R 5  in formula (10). 
       
         
           
           
               
               
           
         
       
     
     
       7. The curable composition as claimed in  claim 1 , wherein the thiol compound derivative is a compound represented by the following formula (15) 
       
         
           
           
               
               
           
         
       
       wherein X 1  is a group represented by the formula (2), and R 5  is the same as R 5  in formula (10). 
       
         
           
           
               
               
           
         
       
     
     
       8. The curable composition as claimed in  claim 1 , wherein the thiol compound derivative is a compound represented by the following formula (16): 
       
         
           
           
               
               
           
         
       
       wherein X 1  is a group represented by the formula (2), M is an alkali metal or an alkaline earth metal, and R 5  is the same as R 5  in formula (10). 
       
         
           
           
               
               
           
         
       
     
     
       9. The curable composition as claimed in  claim 1 , wherein in the formulas (2) and (17), A is an oxygen atom, R 1  is a hydrogen atom, R 2  is an alkyl group or a residue wherein a hydroxyl group is removed from (poly)alkylene glycol, and R 3  is a hydrogen atom. 
     
     
       10. The curable composition as claimed in  claim 3 , wherein the formulas (2) and (17) are each represented by the following formula (7): 
       
         
           
           
               
               
           
         
       
       wherein n is 3 or 4. 
     
     
       11. The curable composition as claimed in  claim 1 , wherein the halogen-containing crosslinking polymer is an acrylic rubber. 
     
     
       12. The curable composition as claimed in  claim 1 , wherein the halogen-containing crosslinking polymer is an epichlorohydrin rubber. 
     
     
       13. The curable composition as claimed in  claim 1 , wherein the halogen-containing crosslinking polymer is a chloroprene rubber. 
     
     
       14. The curable composition as claimed in  claim 1 , wherein the halogen-containing crosslinking polymer is chlorosulfonated polyethylene. 
     
     
       15. The curable composition as claimed in  claim 1 , containing an organic acid metal salt. 
     
     
       16. The curable composition as claimed in  claim 15 , wherein the organic acid metal salt is an organic acid alkali metal salt and/or an organic acid alkaline earth metal salt. 
     
     
       17. The curable composition as claimed in  claim 15 , containing a vulcanization supplement accelerator. 
     
     
       18. The curable composition as claimed in  claim 17 , wherein the vulcanization supplement accelerator is an onium salt and/or polyalkylene oxide. 
     
     
       19. The curable composition as claimed in  claim 1 , containing:
 an amine type anti-aging agent, and 
 a sulfur compound or a phosphorus compound. 
 
     
     
       20. A molded product obtained by crosslinking the curable composition of  claim 1 .